CN108311714A - A kind of micron-size spherical Pt-Ru alloy powder, preparation method thereofs - Google Patents
A kind of micron-size spherical Pt-Ru alloy powder, preparation method thereofs Download PDFInfo
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- CN108311714A CN108311714A CN201711367679.8A CN201711367679A CN108311714A CN 108311714 A CN108311714 A CN 108311714A CN 201711367679 A CN201711367679 A CN 201711367679A CN 108311714 A CN108311714 A CN 108311714A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
The invention discloses a kind of preparation method of micron-size spherical platinum-ruthenium alloys powder, the particle size range of prepared micron order Pt Ru alloy powders is 14 μm, and the average-size of particle is 2.5 μm, specific surface area ranging from 0.1 42m of Pt Ru alloy powders2/g.The present invention uses ammonium chloroplatinate [(NH4)2PtCl6] and ruthenium hydrochloride ammonium [(NH4)2RuCl6] presoma as platinum-ruthenium alloys powder, pass through to be spray-dried to combine and lead to hydrogen reduction, micron order Pt Ru alloy powders are made.By being spray-dried and leading to hydrogen reduction average-size is made about in 2.5 μm of Pt Ru alloy powders, this preparation process is simple for process, and operability is higher, while also avoiding the introducing of impurity in the present invention.
Description
Technical field
The invention belongs to the technical fields of noble metal powder metallurgy, and in particular to a kind of micron-size spherical Pt-Ru alloyed powders
Preparation method.
Background technology
Pt-Ru alloy powders are widely used as catalyst in fuel cell field, in terms of mithridatism, Pt-
Ru alloy catalysts have better performance, especially resisting CO poisoning than independent Pt metal catalyst.Into 21
Century, environmental protection concept are increasingly deepened, and the development of new energy is also brought into schedule, wherein using methanol fuel cell as the new energy of representative
It is concerned, and anode catalyst of the platinum-ruthenium alloys as fuel cell, it is also furtherd investigate, especially some support types
Platinum-ruthenium alloys catalyst, wherein most typical is exactly Pt-Ru/C catalyst.For platinum ruthenium catalyst, if the size of particle is got over
Small, distribution is more uniform, loads to subsequent and obtains uniform product all and can be very helpful.Therefore research platinum-ruthenium alloys
Powder how to possess dispersion evenly, the smaller metallic of particle size have practical value.
The system of polymer-supported catalyst electrode (Pt or Pt-Ru) in a kind of fuel cell of 1 disclosure of the invention of patent document
Preparation Method.This method replaces traditional carbon body material as the load of catalyst using the conductive polymer polyanilinc of high stability
Body, and activation process is carried out by the support layer to electrode, it is polymerizeing polyaniline on electrode support layer using chemical method,
Pt or Pt-Ru are made with electrochemical deposition method, and deposited in polyaniline.But the patent does not indicate obtained Pt
Or the size and shape of Pt-Ru.
A kind of preparation method of the ruthenium-core platinum-shell film with high catalytic performance of 2 disclosure of the invention of patent document.Its step
It is first to recycle two step wet methods electro-deposition Ru films on gold later, then in Ru films in semicircle silicon column reflection bottom face chemical gilding
It is upper to cover Pt layers using spontaneous deposition method, it repeats the above steps, obtains Ru@Pt nano-film electrodes.Although the method platinum ruthenium
Film instead of alloy, and can be directly used for live ATR-SEIRAS research electro-catalysis absorption and effect, but this side
The operating process of method is more complicated, is unfavorable for its industrialized production.
A kind of method of the preparation of high catalytic activity Pt-Ru alloys of 3 disclosure of the invention of patent document.The sources Pt in this method
It is respectively from chloroplatinic acid and hydrate ruthenium trichloride with the sources Ru, solution is formed with amphiphilic block copolymer P123, water, ethyl alcohol and causes
Crystalline substance is restored under the conditions of ultrasonic water bath using ascorbic acid, and high catalytic activity is being obtained by washing, centrifugation, calcining
Pt-Ru alloy catalyst products.
Patent document 1：CN1243389C
Patent document 2：CN100557873C
Patent document 3：CN103933975A
Invention content
The purpose of the present invention is to provide a kind of preparation methods of micron-size spherical Pt-Ru alloy powders, are ensureing Pt-Ru
Under the premise of alloy powder microscopic appearance, the specific surface area of Pt-Ru alloy powders is improved as possible.
Particle size range is at 1-4 μm in Pt-Ru alloy powders, and average-size is about 2.5 μm, and specific surface area is ranging from
0.1-42m2/ g, microscopic appearance are spherical shape.
The present invention is with (NH4)2RuCl6(NH4)2PtCl6For raw material, carried out using spray drying and logical Process of Hydrogen Reduction micro-
The preparation of meter level ball-type Pt-Ru alloy powders.Specific steps are as follows：
(1) it is spray-dried：With (NH4)2RuCl6(NH4)2PtCl6For raw material, it is in the atomic ratio of pt atom and ruthenium atom
1:Under the premise of 1, corresponding weight is weighed, solution is configured to, using the method for spray drying, control flow quantity is 4.0~
6.0ml/min, atomization air pressure be 0.4~0.7MPa, inlet temperature be 140~240 DEG C, hot air flow amount be 4.0~
10.0L/min prepares the precursor powder of platinum-ruthenium alloys.
(2) lead to hydrogen reduction：It by uniform spherical precursor powder in hydrogen atmosphere, is calcined, temperature is controlled 250
DEG C -650 DEG C, in 60-180min micron-sized Pt-Ru alloy powders are made, average-size is about 2.5 μ in soaking time control
m。
Description of the drawings
Fig. 1 is the process flow chart of the present invention
Fig. 2 is the XRD diagram of Pt-Ru alloy powders
Fig. 3 is the (NH after spray drying4)2RuCl6(NH4)2PtCl6The SEM of powder schemes
Fig. 4 is the SEM figures of the Pt-Ru alloy powders after different temperatures calcining
The present invention is described in more detail with specific implementation method below in conjunction with the accompanying drawings.
Specific implementation mode
Embodiment 1
Micron order ball-type Pt-Ru alloy powder preparation processes of the present invention are as follows：
1, it is spray-dried：With (NH4)2RuCl6(NH4)2PtCl6For raw material, it is in the atomic ratio of pt atom and ruthenium atom
1:Under the premise of 1, corresponding weight is weighed, solution is configured to, using the method for spray drying, control flow quantity is 5.0ml/
Min, atomization air pressure 0.7MPa, inlet temperature be 180 DEG C, hot air flow amount be 10.0L/min, be made be uniformly mixed
(NH4)2RuCl6(NH4)2PtCl6For powder, granule size at 1-4 μm, its microscopic appearance is as shown in Figure 3.
2, lead to hydrogen reduction：In a hydrogen atmosphere by uniform spherical precursor powder, it in tube furnace, is calcined, temperature
Degree control at 650 DEG C, soaking time 180min is cooled down under conditions of nitrogen, the size range of particle at 1-4 μm,
Specific surface area is 28.8m2/ g, its microstructure is as shown in fig. 4 a.
Embodiment 2
Compared with Example 1, the technological parameter for manufacturing presoma is identical, the difference is that calcination temperature is 550 DEG C, powder
The soaking time of body is 150min, and for the size range of particle at 1-4 μm, its microstructure is as shown in Figure 4 b.
Embodiment 3
Compared with Example 1, the technological parameter of manufacture presoma mixed-powder is identical, the difference is that calcination temperature is
450 DEG C, the soaking time of powder is 120min, and the size range of particle is at 1-4 μm, its microstructure is as illustrated in fig. 4 c.
Embodiment 4
Compared with Example 1, the technological parameter for manufacturing presoma is identical, the difference is that the calcination temperature of powder is
350 DEG C, soaking time 90min, the size of particle is at 1-3 μm, its microstructure is as shown in figure 4d.
Embodiment 5
Compared with Example 1, the technological parameter for manufacturing presoma is identical, the difference is that the calcination temperature of powder is
250 DEG C, soaking time 60min, the size of particle is at 1-3 μm, its microstructure is as shown in fig 4e.
Comparative example 1
In embodiment 2, the specific surface area of obtained alloy powder is 33.5m2/ g, in embodiment 3, obtained alloy powder
Specific surface area be 37.9m2/ g, in embodiment 4, the specific surface area of powder is 40.0m2/ g, the ratio table of the powder in embodiment 5
Area is 42.0m2/g.During from embodiment 1 to embodiment 5, although it is observed that with temperature reduction particle
Change in size unobvious, but the hole on particle obviously becomes more with fold.
Claims (6)
1. a kind of preparation method of micron-sized Pt-Ru alloy powders, it is characterised in that：Micron is prepared using spray drying technology
The presoma of grade Pt-Ru alloy powders, specifically contains following processing step：
With (NH4)2RuCl6(NH4)2PtCl6For raw material, a certain proportion of (NH is configured4)2RuCl6(NH4)2PtCl6Solution,
Using spray drying process, control flow quantity is 4.0~6.0ml/min, and atomization air pressure is 0.4~0.7MPa, inlet temperature 140
~240 DEG C, hot air flow amount is 4.0~10.0L/min, uniform spherical precursor particle is made, average-size is about 2
μm, high-temperature calcination is carried out to precursor powder followed by the method for logical hydrogen reduction.
2. the preparation method of micron order Pt-Ru alloy powders according to claim 1, it is characterised in that：The micron
Grade high temperature lead to hydrogen reduction method be：Precursor spherical particle is calcined in hydrogen atmosphere, temperature is controlled at 250 DEG C -650
DEG C, in 60-180min micron-sized Pt-Ru alloy powders are made, average-size is about 2.5 μm in soaking time control.
3. the preparation method of micron-sized Pt-Ru alloy powders according to claim 1, it is characterised in that：Described is micro-
The specific surface ranging from 0.1-42m of meter level Pt-Ru alloy powders2/g。
4. a kind of micron order ball-type Pt-Ru alloy powders prepared by method as described in claim 1, it is characterised in that：Powder
Grain is ball-type, and the particle size range of particle is 1-4 μm, and average-size is about 2.5 μm, the ratio table of micron order Pt-Ru alloy powders
Face ranging from 0.1-42m2/g。
5. a kind of preparation method of micron-sized Pt-Ru alloy powders, it is characterised in that：Steps are as follows for specific method：
(1), it is spray-dried：With (NH4)2RuCl6(NH4)2PtCl6For raw material, a certain proportion of (NH is configured4)2RuCl6With
(NH4)2PtCl6Solution, using spray drying process, control flow quantity is 4.0~6.0ml/min, atomization air pressure is 0.4~
0.7MPa, inlet temperature are 140~240 DEG C, and hot air flow amount is 4.0~10.0L/min, and uniformly mixed spherical shape is made
(NH4)2RuCl6(NH4)2PtCl6Particle, average-size is about at 2 μm；
(2), lead to hydrogen reduction：Uniformly mixed spheric granules is calcined in hydrogen atmosphere, temperature is controlled in 250-650
DEG C, micron-sized Pt-Ru alloy powders are made in 60-180min in soaking time control.The present invention is by being spray-dried and leading to hydrogen
Average-size is made about in 2.5 μm of Pt-Ru alloy powders in reduction.
6. a kind of preparation method of micron-sized Pt-Ru alloy powders, it is characterised in that：Specifically contain following processing step：
(1) it is spray-dried：With (NH4)2RuCl6(NH4)2PtCl6It is 1 in the atomic ratio of pt atom and ruthenium atom for raw material:1
Under the premise of, corresponding weight is weighed, solution is configured to, using the method for spray drying, control flow quantity is 5.0ml/min,
Atomization air pressure is 0.7MPa, and inlet temperature is 180 DEG C, and hot air flow amount is 10.0L/min, and uniformly mixed (NH is made4)2RuCl6(NH4)2PtCl6Powder, granule size is at 1-4 μm；
(2) lead to hydrogen reduction：In a hydrogen atmosphere by uniform spherical precursor powder, it in tube furnace, is calcined, temperature control
System is at 650 DEG C, and soaking time 180min is cooled down under conditions of nitrogen, and the size range of particle compares table at 1-4 μm
Area is 28.8m2/g。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110000370A (en) * | 2019-04-19 | 2019-07-12 | 贵研铂业股份有限公司 | A kind of Large ratio surface iridium is black and preparation method thereof |
| CN111168080A (en) * | 2020-01-17 | 2020-05-19 | 陕西瑞科新材料股份有限公司 | Preparation method of nano platinum metal |
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| CN105458278A (en) * | 2015-12-08 | 2016-04-06 | 贵研铂业股份有限公司 | Preparation method of high-purity spherical ruthenium powder |
| CN105834457A (en) * | 2016-05-27 | 2016-08-10 | 贵研铂业股份有限公司 | Preparation method for micro-grade spherical Mo-Ru brazing filler powder |
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| JPS6438144A (en) * | 1987-08-04 | 1989-02-08 | Kansai Coke & Chemicals | Production of catalyst for synthesizing hydrocarbon |
| CN101102845A (en) * | 2004-11-03 | 2008-01-09 | 国际壳牌研究有限公司 | Attrition resistant particulate catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110000370A (en) * | 2019-04-19 | 2019-07-12 | 贵研铂业股份有限公司 | A kind of Large ratio surface iridium is black and preparation method thereof |
| CN111168080A (en) * | 2020-01-17 | 2020-05-19 | 陕西瑞科新材料股份有限公司 | Preparation method of nano platinum metal |
| CN111168080B (en) * | 2020-01-17 | 2023-03-24 | 陕西瑞科新材料股份有限公司 | Preparation method of nano platinum metal |
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